Process for breaking petroleum emulsions, certain oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins and method of making same



ateant 2,771,453 Patented Nov. 20, 19 56 ffioe Melvin De Groote, University City, and Kwane'ling Sheri, Brentwood, M0,, assignors to Petrolite Corporation, Wilmington, Del, a corporation of Delaware No Drawing. Application July 30, 1953, Serial No. 371,412

20 Claims (Cl. 252344) The present invention is a continuation-in-part of our co-pending application, Serial No. 364,503, filed June 26, 1953.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the waterin-oil type that are commonly referred to as cut 'oil,

lea

roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under.- w

controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and, subsequent demulsification under the conditions just mentioned are of significant value intomoving impurities, particularly inorganic salts, from pipe- 7 hyde followed by reacting this product with ethylene,

propylene, or butylene oxide, glycide, or mixtures thereof, and with the use of two moles of the resin condensate to one mole of the polyepoxide, the polyepoxide being non-aryl, as more fully explained hereafter.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but, in fact, are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in producing the compositions used in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be non'aryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 364,503, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equipment compound such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides'have been described in the literature and particularly the patent literature. See for example, Italian Patent No. 400,973, dated August 8, 1951; see, also, British Patent 518,057, "dated December 10, 1 938; and U. S. Patent No. 2,070,990 dated February 16, 1937 to Gross et al. Reference is made also to U. S. Patent 2,581,464, dated January 8, 1952,. to Zech. This particular last mentioned patent describes a composition of the following general formula:

' O [mammal in which x is at least 1, z varies from less than 1 to more than 1, and x and z together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaiuing after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above formula, and any remaining groups of the residue being free hydroxyl groups.

It is obvious from what is said in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl radical; thus, theformula would become Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus difierentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the. solvent selected would have to be one which is not susceptible to oxyalkylation as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents,

dibutyl ether, dihexyl ether, ethyleneglycol diethylether, V

simplest diepoxide which contains at least 4 carbon atoms and is formally described as l,2-epoxy-3,4-epoxybutane(1,2-3,4 diepoxybutane). 7

It well may be that even though the previously sug- They usually represent, of course, 1,2

gested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenolaldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, 'i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and usually less than 4, and including .0, and R represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization "condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, gluconic acid, etc. In. other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in the instance is to differentiate from insoluble; resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from'any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products before and after treatment with a polyepoxide reveals that the polyepoxide by and large introduces increased hy-' drophilecharacter or, inversely, causes a decrease in hydrophobe character. However, the solubility characteristics of the final product, i. e., the product obtained by oxyalkylation with a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, or propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in the solubility characteristics or in the hydrophobe hydrophile character so as to be about the same as prior to oxyalkylation with the monoepoxide.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylenesoluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such .test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the refer- .ence in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what "is said hereinafter Will be divided into seven parts:

Part 1 is concerned with the hydrophile nonaryl poly- 'epoxides and particularly diepoxide's employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation to yield the amine-modified resin;

Part 3 is concerned with basic nonhydroxylated polyamincs having at least one secondary amino group and 'having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides, and particularly diepoxides;

Part 5 is concerned with reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than reaction between 2 moles of a previouslyprepared amine-modified phenol-aldehyde resin condensate as described and one mole of a hydrophile polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 6 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 5, preceding, i. e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl others may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by 'etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990,

dated February 16, 1937, to Groll, and is of the following formula The diepoxides previously described may be indicated by the following formula:

in which R represents a hydrogen atom or methyl radi- "cal R. represents the rlival'entradi'ca l uniting alent thereof in that the epichlorohydrinitself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl 'epichlorohydrin. So presented the formula becomes:

H H H V H H H 5HC-OG-OI:R1]O-OCOH O O In the above formula R1 is selected from groups .such as the following:

C2H4 C2H4OC2H4 C2H4OC2H4OC2H4 CsH's CsHeOCsHe CsHeOCaHsOCsHs Cal-Ia 'C4H8OC4HB C4HaOC4HaOC4Hs -C3H5(OH) CsHa(OH)'GC3H5(OI-l) CsH5(OH)OC3H5(OH)OC3H5(OH) It is to be noted that in the above epoxide's'ther'e is a complete absence of (a) aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R1 is inherently hydrophile in character as indicated by the factthat it is specified that the precursory diol or polyol OHROH must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as H H H H H H HCCCORO-CC-OH E H is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by OC- (H Thus, R(OH)1w Where n represents a small whole numher which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula H H II H H H in which R1 is C3H5(OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure'would produce 'a triepoxide or, similarly, if R happened to be CaH5(OH)OC3I-I5(OH), one could obtain a tetraepox-ide. Actually, such procedure generally yields vtriepoxide, or mixtures with higher epoxides'and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, 01', stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin' so as to give the appropriate diepoxide. The

.molecular weight is approximately 370 and the number .of epoxide groups per molecule are approximately 2. For

this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorhydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyg lycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

See also Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula H H OH R R n R In the above formula n represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably or 12 units, particularly when the resin is subjected .any other reactive aldehyde having 8 carbon atoms or less. a

-Because a resin is organicsolvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are. derived from trifunctional phenols as previously noted. '.However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenatedsolvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that'all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned US. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated polyamine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

OH OH OH OH OH OH H r H H H r .1 0- O C C 0- H H H H H R R n R R R K As has been pointed out previously, as far as the resin unit goes one can use a mole of aldheyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

. R R R in which R'" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as .a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10th of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins We found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. wt. Ex- R of resin ample R Position derived n molecule number of R from- (based on n+2) Phenyl Para. Formal- 3. 5 992. 5

dehyde. Tertiary butyl do. ..do. 35 882. 5 Secondary butyl. 3. 5 882. 5 Oyclo-hexyl P 3.5 1, 025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805.5

and tertiary amyl.

1 3. 5 805. 5 Tertiary hexyl. 3.5 1, 036.5 ct 1 3. 5 1, 190. 5 Nonyl- 3. 5 1, 267. 5 Decyl. 3. 5 1, 344. 5 Dodecy 3. 5 1, 498. 5 Tertiary butyl 3. 5 945.

Tertiary amyl 3. 5 1, 022. ony 3.5 1, 330. Tertiary butyl 3. 5 1, 071.

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1, 456. 5 3. 5 1,008. 5

Tertiary amyl 3. 5 1, 085. 5 onyl- 3. 5 1,393.5 Tertiary buty 4. 2 996.6

4.2 1, 083. 4 Nonyl 4. 2 1, 430. 6 Tertiary butyl. 4. 8 1, 094. 4 Tertiary amyl. 4. 8 1,189. 6 Nonyl 4. 8 1, 570. 4 Tertiary amyl- 1. 5 604. Gyclo-hexyl. 1. 646. 0 1. 5 653. 0 1. 5 688. 0

2.0 692. 0 Hexyl 2. O 748. 0 Cyclo-hexyl 2.0 740. 0

, 1.0 7 PART 3 I I As has been pointedout, the amine 'hefein employed as a reactant is a .basic secondary polyamine :and' preferably a strongly basic secondary polyamine 'free from hydroxyl groups, free from primaryamino groupsyf-ree from substituted imidazoline groups, and free fromsubstituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl alicyclic, arylalkyl, or heterocyclic in character. Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polyprop lene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to termial alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. 'In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or.one terminal :group could be converted into a tertiary group and the other 'into a secondary amino group. By way of example the following formulas are included.

the divalent radical has a carbon atom chain interrupted N CaHiN CzHsN H H N 0 140 0 gHrN 0 {H5 V 02115 N c.1540 CzEhN \H CH2\ H N propyleneNpropyleneN Another procedure for producing .suitable polyami'nes is a reaction involving first an alkylene imine, such .as

ethylene imine or propylene imine, followed by an What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine,

such as dibutylamine, dibenzylamine, dicyclohexylamine,

or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such a dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to.convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an etherlinkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

' [R' (O CnHIn) :11?!

in which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to l, with the proviso that the sum of m plus m equals 2', and R has its prior significance, particularly as a hydrocarbon radical.

Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition R-O (CH2);

as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may i be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustrating it may be well to refer again to the fact that previously the amine was shown as R! with the statement that such presentation is an oversimplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may react to two different positions and thus the same amine may yield compounds in which R and R' are dissimilar. This is illustrated by reference to two prior examples: 1

' CH: 7 H OH;

NpropyleneNpropyleneN 12 In the first of the two above formulas if the reaction in,- volves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two difierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

CH5 CH3 H H H NCzH4NC2H4NCgH4NCaH4 H CH3 Over and above the specific examples which have appeared previously, attention is directed to the fact that.

added suitable polyamines are shown in subsequent Table II.

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since'the resin molecule cannot be defined satisfactorily by formula,

although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact thatthe procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine.

aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removedreadily at a comparatively mod- --more suitable than others. we have found xylene the most satisfactory solvent.

oxygenated solvent such as a low-boiling alcohol, including-ethyl alcohol, methyl alcohol, etc. Higher alcohols can .be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can alsousea mixture. of benzene or xylene and ,such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial-resin-which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system forreaction.

Actually, water is apt tobe present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the .commercialproduct which is approximately 37%, or itmay'be diluted down to about 30% formaledhyde. However,,paraformaldehyde can be used but it is more diflicult perhaps to add a solid material instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. lnany event, water is present as water of reaction. If thesolvent is completely removed at the end of the process, no prob lem is involved if the-material is used for any subsequent reaction.

In the next succeeding paragraph itis pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, 'two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? ('12) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as'in thecase of oxyalkylation? and the third factor is this, (c) is an effort to be made to purify the reaction mass 'by the usual procedure as, for example, a water-Wash to remove the water-soluble unreacted formaldehyde, if any, or a waterwash to remove any unreacted water-soluble .polyamine, if employed and present after reaction? Such procedures are-Wellknown and, needless to say, certain solvents are Everything else being equal,

We have found no particular advantage'in using alow temperature in the early stage of the reaction because,

and for reasons explained, this .is not necessary although it does apply in some other procedures that,'in a general Way, bear some similarity to the present procedure. There is no objection, of course, to giving the'reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in

fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is amatter-of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble then agitation is required only to the extent that it helps cooling or helps distribution of the incomingformaldehyde. This mutualsolubilityisnot. necessary as, previouslypoihted out butmay be convenient under certain circumstances. On the .otherhand, if theproductsare not .mutuallysoluble then agitation should be. more vigorous for the reasonrthat reaction probably takes place principally at the interfaces and the morevigorousthe agitation themore interfacial area. The general procedure employed 'is "invariably the same when adding theresin and-the selected solvent, such as benzene or Xylene. Refluxing should'be long enough to insure that the resin added, preferably in a powdered form, is completelysoluble. 'However, if-the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it mayor may not be soluble 'in theresin solution. If it is not soluble in the resin solution ployed. The formaldehyde .is then added in asu'itable form. For reasons pointed out we prefer to useasolution and whether to use a-commeroial 37% concentration is simplya matter of choice. In large -.scale manufacturing there may be some advantage .in using a 30% solution of formaldehye butapparently this is not true on a small laboratory scale or .pilot plant scale. 30% formaldehyde may tend :to decrease any formaldehyde .loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difiiculty withforrnaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difliculties are involved. 'We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing ,a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on Whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to 10-24 hours, we then complete the reaction by raising the temperature up to 150 C., or .thereabouts as required. The initial low temperature procedure can 'be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then 'permitthe temperature to rise to somewhere about C., and generally slightly above 100 -C. and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reactionmass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner ,in the .same way as the removal of solvents .in resin manufacture as described in aforementioned Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the endproduot showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after ,removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration.

Example 1b The phenol-aldehyde resin is the one which has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

drawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectable the phase separating trap was set so as to eliminate all the water of solution and reaction. part of the xylene was removed until the temperature reached approximately 152 C., or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat less than 30 hours. In other examples, it varied from a little over 20 hours up to 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out-previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt Amine used and amount forrnalde- Solvent used tion, tlon distill. No. used grs. hyde soln. and amt. tomop., time, tern and amt. hrs.

s32 Amine A, 176 g 30%, 200 g-" Xylene, 600 m- 20-23 26 152 480 Amine A, 88 g- 30%, 100 g... Xylene, 450 g 20-21 24 150 633 do do Xylene, 550 gm- 20-22 28 151 441 Amine B, 116 g- 37%, 81 g. Xylene, 400 g 20-28 36 144 480 .do do .1 Xylene, 450 g 22-30 156 633 do t .do Xylene, 600 g 21-28 32 150 882 Am ne O, 204 g 30%, 200 g do 21-23 30 145 480 Ammo O 102 g 37%, 100 g. Xylene, 450 g-- 20-25 148 633 do do Xylene, 500 g 20-27 35 143 473 Amine D 117g Xylene, 425 g 20-22 31 145 511 do Xylene, 500 g 21-26 24 146 665 Xylene, 550 g 22-25 36 151 441 Xylene, 400 g 25-38 32 150 595 Xylene, 550 g 21-26 27 145 441 Xylene, 400 g- 20-23 25 141 480 do 22-27 29 143 5 23-25 36 149 498 o 21-26 32 148 542 Xylene, 500 21-23 30 148 547 -do do 20-26 36 152 441 do Xylene, 440 g 21-24 32 150 595 Amine H, 282 g 37%, 81 g Xylene, 500 g 21-28 25 150 391 Amine H, 141 g 30%, g Xylene, 350 g. 21-22 28 151 882 grams of the resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 ,to 45 C. for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate with- As to the formulas of the above amines referred to as bArlnine A through Amine H, inclusive, see immediately e ow:

After the water was eliminated diepoXi-de' previously designated as diepoxide A, and

H H Amine \NczmNoamN/ condensate 2'5. Condensate 2b was derived from resin II a. Resin 5a, in turn was obtained from tertiary amyl- CH3 CH3 phenol and formaldehyde. ondensate 2b employed as 3L g 5 reactants resin 5a and diethyanolamine. The amount of V of resin employed was 480' grants; the amount of dietha Amme E 0 Notmgctfit noljamine employed was 105 grams, and the amount of o0 37% formaldehyde employed was 81 grams. The amount H2 H2 of solvent (xylene) employed was 450 grams. All this has been described previously. Amine F c 11,; 0 CHQ4NCH2CH2CH2N The solution of the condensate inxylene was adjusted OH to a 5C'% solution. In this particular instance, and in CH CH 3 practically all the others which appear in the subsequent 7 p 3 tables, the examples are characterized by the fact that no Amine G NCiHigOzHt lg z iN alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, mg a small amount of an alkaline catalyst could be added, GET-CH1 CHzCH' such as finel powdered caustic soda, sodium methylate, y I. i 6 CH3O OH HGNEPCzHNEFC HC OCH3 etc. If such alkaline catalyst 1s added it may speed up the reaction, but it may also cause an undesirable re- I 7 01120113 action, such as the polymerization of the diepoxide. A PART 5 In any event, 116 grams of the condensate dissolved cognizance should be taken Of one particular feature in a e y t equal Weight y were Stirred in connection with the reaction involving the polyepoxide I and t d to a little over th bOlllIlg Point of Waterand the amine condensate and that is this: the arninegrams i f l f pfeviflusly lfilentified as modified phenol-aldehyde resin condensate is invariably 130x163 A, and dlsfmved 111 equalflvelghi 9 Xylene, basic and thus one need not add usual catalysts were added dropwise. The initial addition of the xylene which are used to promote such reactions. Generally P P carried thefe'fnlefatilf t0 about C The speaking, the reaction will proceed at a satisfactory rate i f fad h? q PQ P ltaf a ed m 5 a an under suitable conditions without any catalyst at all. Hour 5 time- Dunng l e u tlme the reflux Employing polyepoxides in ccmbinafion with a perature rosetoabout126 Q. The product was allowed basic reactant the usual catalysts include alkaline m fefiltX at ghtly a ve 130 us ng a phase-separatterials such as caustic soda, caustic potash, sodium methylm A $31311 mm? of xylene was removed lay ate, etc. Other catalyst may be acidic in nature and l f 9 eP w a e H8350 t i refluxmg are of the kind characterized by iron and tin chloride. temperfi'tm'e rose gradually approxunately Furthermore, insoluble catalysts Such as clays or specially The mixture was refluxed at thls temperature for a little prepared mineral catalysts have been used If for any less than hours. Experiencehas indicated that thls reason the reaction did not proceed rapidly enough with penod of time sllfftclent compietveqth? E the diglycidyl ether or other analogous reactant, then At the 9. the Penod h Xylene Wh1ch..had a small amount of finely divided caustic soda or sodium 40 reinc'vcd t n the f ff P ne to ma methylate could be employed as a catalyst; The amount mlxmre' A small of matenahwas wlthdrawn a generally employed Wouldbe 1% (yr-2% the xylene evaporated on a hot plate in order to examine It goe without saying that the'reaction can take place l Physlcall pr9pemes' h matengl was a .dark 1 in an inert solvent, it one that is not oxyalkylatiom viscous semi-solid. It was insoluble in water, it was insusceptible. Generally speaking, this is most conveniently $2 1 hi P i as Soluble m Xylene an aromatic solvent such as xylene or a higher boiling i pamcu y m a F OI S Xylene. and coal tar solvent, or else a similar high boiling aromatic methanol .doweyer" 1f the material dissolved i solvent obtained from petroleum. One can employ an anpxygenaied Solvent a than shaken Wlth 5% glucomc oxygenated solvent such as the diethylether of ethylene acldf 1t h fi l .tendency. to dlsperse suspend glycol, or the diethylether of propylene glycol, or'simila'r' arm .31 d. liahnculafly F a xylene'metilanol ethers, either alone or in combination with a hydrocarbon mmed sowent prcvlo-usly descnbed W1 th or Without solvent. The selection of the solvent depends in part gg f gg i f 5 g g 3 1 I hr on the subsequent use of the derivatives or reaction prodcf Wh 11 g f g i i 1g ucts. If the reaction products are to be rendered solvent- Y P4P u m e ec Is i profree and it is necessary that the solvent be readily removed Ce 31m} ar 9 Qy m use of glyclde or as for example by the use of vacuum distillation thus methylglyclde as oxyalky-latmg agents for X H or an ammatic etroleum will serve ample, Part 1 of U. S. Patent No. 2,602,062 dated July Y P 1, 1952, to De Groote.

Exampl 6 Various examples obtained in substantially the same The product was obtained by reaction between the manner are enumerated in the following tables:

TABLE III Gon- Diep- Time Max. Ex. den- Amt., oxide Amt, Xylene, Molar of reactemp, Color and physical state No. sate grs; used grs. grs. ratio tton, 0.

used hrs.

15% 1 i D'arkDbrown Semi-801M. 111 14 181 5 1291 5 221 4 164 D3: 119 A 13. 5 137. 5 2:1 4 170 Do. 120 A 18.5 138.5 2:1 4 165 D0. 159 A 18. 5 177.5 2: 1 4. 5 166 Do. 122 A 18. 5 140. 5 2:1 4. 5 152 Do. 143 A 18.5 161.5 2:1 5' 170 Do. A is. 5 158. 5 2:1 5 165 Do. 146 A 18.5 164.5 2:1 5 Do.

TABLE IV I Con- Time Max. Ex. den- Amt, Diep- Amt, Xylene, Molar of reactem Color and physical state No. sate grs. oxide grs. grs. ratio tron,

used used hrs.

116 B 11 127 2: 1 4 160 Dark brown Semi-solid. 122 B 11 133 2:1. 4 162 Do. 111 B 11 122 2:1 4 158 Do. 119 B 11 130 2: 1 4. 5 162 Do. 120 B 11 131 2:1 4. 5 165 D0. 159 B 11 170 2:1 5 170 Do. 122 B 11 133 2: 1 4 158 Do. 143 B 11 154 2:1 5 164 Do. 140 B 11 151 2:1 5 170 Do. 146 B 11 157 2:1 5 165 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE V Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydrowls used product grs. grs. per moleeule 2, 690 2, 695 l. 350 .13 2, 810 2, 810 l, 405 13 2, 590 2, 590 l, 295 13 2, 750 2, 750 1, 375 13 2, 770 2, 780 1, 395 13 3, 550 3, 550 l, 775 13 2,810 2,830 1,435 13 3, 230 3, 230 1, 615 13 3, 170 3, 180 1, 595 14 3, 290 3, 290 1, 645 14 TABLE VI Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product g'rs. grs. per molecule 2, 540 2, 550 1. 280 11 2, 660 2, 660 1, 330 11 2. 440 2, 440 1, 220 11 2, 600 2, 600 l, 300 11 2, 620 2, 630 l, 320 11 3, 400 8, 400 1, 700 ll 2, 660 2, 660 l, 330 11 3, 080 3, 060 l, 520 11 3, 020 3, 020 l, 510 12 3, 140 3, 140 l, 570 12 At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance 90% or 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine) CH2( Resin) CHz(Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) (lHflResin) CH (Amine)] [D.G.E.l

[(Amine) CH2(Resln) CH (A1nine)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part 5, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal diflerence is only that While polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, i. e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may represent less of a hazard than glycide, yet these reactants should be handled with extreme care. One suitable procedure involves the use of proplyene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which "represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed hydrophile character can be reduced or balanced by use of some other oxide, such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene 21 oxide,- the final product may contain some unreac'ted propylene) oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner. Se'e' article entitled nthylene oxide hazards and methods of handling, Industrial and Engineering Chemistr'y, volume 42, No. 6, June 1950, pp. 1251-1258. Other procedures can be employed as, for example, that described in U. S. Patent No. 2,586,767, dated February 19, 1952, to Wilson.

The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of monoepoxide treated amine-modified phenol-aldehyde condensati'on product.

Example ID The polyepoxide-derived oxyalkylation-susceptible compound is the one previously designated as 1:. Polyepoxide-derived condensate 1c was obtained, in turn, from condensate 2b and diepoxide A. Reference to Table II shows the composition of condensate 212. Table II shows it was obtained from resin 5a, Amine A and formaldehyde. Amine A is symmetrical dimethyl ethylene diamine. Table I shows that resin 5a was obtained from tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oXyalkylation-susceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent prescut at the time of treatment with a monoepoxide is indicated, as stated, on a solventfree basis.

13.45 pounds of the polyepoxide-derived condensate were mixed with 13.50 pounds of solvent (xylene in this series), along with one pound of finely powdered caustic soda as a catalyst. The reaction mixture was treated with 4.5 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 20.4 to one, and the theoretical molecular weight was approximately 3600.

Adjustment was made in the autoclave to operate at a temperature of about 125 C. to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the oxide in approximately /2 hour and then continue stirring for a half-hour longer, simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide probably could have been injected in 15 minutes instead of an hour and the subsequent time allowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables VII, VIII and 1X.

The size of the autoclave employed was gallons. In innumerable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 2D This simply illustrates further oxyalkylation of Example '22 1D, preceding. The oxyalkylation-susfit'ible edmpoima 1c is the same as the one used in Example 1]), preceding, because it is merely a continuation; In subsequent tables; such as Table VII the oxyal kylatidn-suscepitible co'm pound in the horizontal line concerned Example 213 refers to oxyalkylati'on-susceptible compound 10. Actually, one could refer just as properly to exempts ID at stage. It is immaterial which designation is used so long as it is understood such practiceis' used consistently throughout the tables. In any event, the, amount of ethylene oxide introduced was less than previously, to wit, only 4.5 pounds. This meant the amount of oxide at the end of the stage was 9.0 pounds, and the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 408 to 1 The theoretical molecular weight was 4500. There no added solvent. In other words, it remained the same, that is, 13.50 pounds and there was no added catalyst. The entiresproce'dure was substantially the same as in Example- 1D, preceding.

In this, and in all succeeding examples, the time and pressure were the same as previously, to wit, tn C., and the pressure 10 0 15 pounds; The time element was only one-half hour because considerably less oxide was added.

Example 3D The oxyalkylation proceededin the same manner as in Examples 1D and 2D. There was no added solvent and no added catalyst. The amount of oxide added was 4.45 pounds. The total amount of oxide at the end of the stage was 13.45 pounds. The molal ratio of oxide to condensate was 61 to l. The theoretical molecular weight was approximately 6300, and as previously noted the time period, temperature and pressure were the same as in preceding Example 2D.

Example 4D The oxyalkylation was continued and the amount of oxide added was practically the same as" before, to wit,; 4.55 pounds. The amount of oxide added at the end of the reaction was 18.00 pounds. There was no added solvent and no added catalyst. Conditions as far asv temperature and pressure are concerned were the same: as in previous examples. The time period was slightly' longer, to wit, 45 minutes. The reaction at this point showed modest, if any, tendency to slow up. The molalt' ratio of oxide to oxyalkylation-susceptihle compound was. 81.6 to 1. The theoretical molecular weight was 6300- Example 5D The oxyalkylation was continued with the introduction of another 7.9 pounds of oxide. No added solvent was introduced and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the re action was approximately 8100. The molal ratio of oxide to oxyalkylation-susceptible compound was 122.4 to 1. The time period was 1% hours.

Example 6D The same procedure was followed as in the previous examples without the addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 9.1 pounds. The amount of oxide at the end of the reaction was 36.0 pounds. The time required to complete the reaction was the same as pre- In substantially every case a 35-gallon massive was 23 employed, although in some instances the initial oxyethylation was started in a -gallon autoclave and then transferred to a 25-gallon autoclave, or at times to the -gallon-autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda. 7

Referring to Tables VII, VIII and IX, it will be noted that compounds 1D through 18D were obtained by the use of ethylene oxide, whereas Examples 19D through 36D were obtained by the use of propylene oxide; and Examples 37D through 54D were obtained by the use of butylene oxide. I 7

Referring now to Table VIII specifically, it will be noted that the series of examples beginning with 1E were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 6D as the oxyalkylation-susceptible compound. This applies to series lE through 18E.

Similarly,'sen'es 19E through 36E involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 1913 was prepared from 24D, 2. compound which was initially derived by use of propylene oxide.

Similarly, Examples 37E through 54E involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first- Also, these two oxides Were used in the series 5513'. through 72E, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73E through 90E involve the use of propylene oxide and buylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1F through 18F the three oxides were used. It will be noted in Example IF the initial compound was 78E; Example 78E, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1F through 6F was by use of ethylene oxide as indicated in Table IX.

Referring to Table IX, in regard to Example 19F it will be noted again that the three oxides were used and 19F was obtained from 60E. Example 60E, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19F and subsequent examples, such as 20F, 21F, etc., propylene oxide was added.

Tables X, XI and XII give the data in regard to the oxyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table VII in greater detail, the data are as followsi The first column gives the example numbers, such as 1D, 2D, 3D, etc. etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1D through 6D, is Example 10, although it would be just as proper to say that in the case of 2D the oxyalkylatierr-susceptible compound was 1D, and in the case of 3D the oxyalkylationsusceptible compound was 2D; Actually, reference is to the parent derivativefor the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the epoxidederived condensate previously referred to.

'The fourth column shows the amount of ethylene oxide in themixture prior to the particular oxyethylation step. In the caseof Example 1D there is no oxide used but it appears, of course, in 2D, 3D, and 4D, etc.

'The fifth column can be ignored forthe reason that it is concerned with propylene oxide only, and the sixth column can be ignoredfor the reason that it is concerned with. butylene oxide only.

The'seventh column shows the catalyst which is invariably powdered caustic. soda.

The eighth column shows the amount of solvent which is xylene unless otherwise stated. i 7

'24 The ninth column shows the oxyalkylation-susceptible compound which in this series is the polyepoxide-derived condensate. 1 7 l i. I ,t The tenth column shows the amount of ethylene, oxide in at the end of the particular step. I

Column eleven shows the same data for propylene' oxide and column twelve shows data for butylene oxide. For obvious reasons these can be ignored in the series 1D through 18D.

Column thrirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the solvent at the end of. the oxyalkylation steps The fifteenth, sixteenth and seventeenth columns. are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used inthe present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature,

Referring now to the second series of compounds in Table VII, to wit, Examples 19D through 36D, the situation is the same except that it is obvious that the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the r fifteenth column becomes a blank, but column five, which oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene'oxide present at the end :of the reaction, and column sixteen carries rata as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37D through 54D 'in Table VII, columns four and five are blanks, column ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to butyleneoxide present before the particular oxyalkylation step: Column twelve gives the amount of butylene oxide'prescut at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible com pound.

Table VIII is in essence the data presented inexactly the same way except the two oxides appear, to wit, ethyl-i ene oxide and propylene oxide. are only three columns in which data does not appear, all three being concerned with the use of butylene oxide Furthermore, it shows which oxide was used first by the very fact that reference to Example 1E, in turn, refers-to 6D, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of compari-' son and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate 10.-

This is obvious, of course, because the figures 103.2 and 46.5 coincide with the figures for 6D derived from lc shown in Table VII. 7 V

In Table VIII (Examples 19E through 36E) thejsame situation is involved except, of course, propyleneoxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37E and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first.

nv rs E amp S a du e n er s re s This means that there" the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73B and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with 1F, Table IX, particularly 2E, 3F, etc., show the use or" all three oxides so there are no blanks as in the first step of each stage where one oxide is missing. It is not believed any further explanation need be oilered in regard to Table IX.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides, had be duplicated when used subsequently for further reaction. It ,vould be confusing to refer to too much detail in these various tables for the reason that all the data appear in considerable detail and is such that: all results can be readily shown.

Reference to solvent and amount of alkali at any point takes into consideration the. solvent from the previous step and the alkali left from this step. As previously pointed out, Tables X, XI and give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1D through 6D.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the Tables. If desired, the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined 26 oxide, if present and volatile under the conditions em ployed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but on can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., not attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides, just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber or a straw color, or even a pale straw color. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product that the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent.

TABLE VII Composition before Composition at end Oxides Ex. No. 050, OSC, Cata- Sol- 080,

ex. lbs. lyst, vent, lbs. No. EtO, PrO, BuO, lbs. lbs.

lbs. lbs. lbs.

EtO

Molal ratio EtO to Pro to BuQto vst, vent, 0 rue]. lbs. lbs. l wt.

alkyl. alkyl. alkyl. suscept. suscept. Suscept. ompd. crnpd. cmpd.

U! -u I z r s e s s sm Ocpznccucoooouooocnom TABLE IX Composition berm-e Compositiofi at end E Oxides 'Oxide's Molal ratio x. No. O80, O80, Cata- Sol- 030, Cata- Sol- Theo.

ex. lbs. lyst, vent, lbs. lyst, vent, J f 3 8, 3 g f mol. N0. EtO, PrO, BuO, 1m. lbs. EtO, PrO, BuO, lbs. lbs. alkgl wt.

lbs. lbs. lbs. lbs. lbs. s. y y

suscept. suscept. suscept. cmpd. cmpd. cznpd.

81. 0 27. 0 1. 13.5 13. 4. 5 81. 0 27.0 1. 5 13. 5 20. 4 279.0 83.4 25, 187 4. 5 81. 0 27. 0 1. 5 13. 5 13.45 9.0 81. 0 27. 0 1. 5 13. 5 40.8 279.0 83. 4 26, 085 9.0 81.0 27.0 1.5 13. 5 13.45 13.5 81.0 27.0 1. 5 13.5 61. 2 279.0 83.4 26, 982 13. 5 81. 0 27. 0 1. 5 13. 5 13.45 18.0 81. 0 27. 0 1. 5 13. 5 81. 6 279. 0 83.4 27, 880 18.0 81. 0 27. 0 1. 5 13. 5 13.45 22. 5 81. 0 27.0 1. 5 13.5 102.0 279.0 83.4 28, 777 22. 5 81. 0 27.0 1. 5 13.5 13.45 27.0 81.0 27.0 1. 5 13. 5 122. 4 279. 0 83. 4 29, 675 35.0 63. 0 1. 5 14. 05 14.05 5. 0 35.0 63.0 1. 5 14. 05 22. 7 120. 63 175.05 23, 410 5. 0 35.0 63. 0 1. 5 14.05 14. 05 10. 0 35.0 63. 0 1. 5 14.05 45. 4 120. 63 175.05 24, 410 10.0 35.0 63.0 1. 5 14.05 14. 05 15. 0 35. 0 63.0 1. 5 14.05 68. 1 120. 63 175.05 25, 410 15. 0 35.0 63.0 1. 5 14.05 14.05 20. 0 35.0 63.0 1. 5 14.05 90. 8 120. 63 175.05 26, 410 20.0 35.0 63. 0 1. 5 14.05 14.05 25. 0 35.0 63. 0 1. 5 14. 05 113. 5 120. 63 175.05 27, 410 25.0 35.0 63. 0 1. 5 14.05 14. 05 30.0 35. 0 63.0 1. 5 14.05 136. 2 120. 63 175.05 28, 410 39.0 65. 0 1. 5 12. 95 12.95 6. 5 39.0 65. 0 1. 5 12. 95 29. 5 134. 4 180. 5 24, 690 6. 5 39.0 '65. 0 1. 5 12. 95 12. 95 13.0 39.0 65.0 1. 5 12. 95 59.0 134. 4 180. 5 24, 690 13.0 39.0 65. 0 1. 5 12.95 12.95 19. 5 39. 0 65.0 1. 5 12. 95 88.5 134. 4 180. 5 27. 290 19. 5 39.0 65.0 1. 5 12. 95 12. 95 26. 0 39.0 65.0 1. 5 12. 95 118.0 134. 4 180. 5 28, 590 26.0 39.0 65.0 1. 5 12.95 12.95 32. 5 39.0 65.0 1. 5 12. 95 147 5 134.4 180. 5 29, 890 32. 5 39. 0 65.0 1. 5 12.95 12.95 39. 0 39.0 65.0 1. 5 12. 95 177. 0 134.4 180. 5 31,190 54. 0 54.0 1. 5 13. 5 13.45 54. 0 6. 75 54.0 1. 5 13. 5 244. 8 23. 25 166. 8 28, 920 54. 0 6.75 '54. 0 1. 5 13. 5 13.45 54. 0 13. 54. 0 1. 5 13. 5 244. 8 46. 50 166. S 30, 270 54. 0 13.50 54. 0 1. 5 13. 5 13.45 54.0 20.25 54.0 1. 5 13. 5 244.8 69. 166.8 620 54. 0 20. 25 54. 0 1. 5 13. 5 13. 45 54. 0 27.0 54.0 1. 5 13. 5 244.8 93.0 166. 8 32, 970 54.0 27. 0 54.0 1. 5 13.5 13.45 54.0 40. 5 54. 0 1. 5 13.5 244.8 139. 5 166. 8 35, 670 54. 0 40.5 54. 0 1. 5 13. 5 13.45 54. 0 54. 0 54.0 1. 5 13. 5 244. 8 186. 0 166. 8 38, 370 30. 0 2l. 0 1. 5 14. 05 14. 05 30. 0 7.0 21.0 1. 5 14.05 136. 2 24. 58. 35 14, 410 30. 0 7. 0 21. 0 1. 5 14. 05 14.05 30. 0 14.0 21. 0 1. 5 14.05 136. 2 48. 25 58. 35 15. 810 30. 0 14. 0 21. 0 1. 5 14. 05 14. 05 30. 0 21.0 21.0 1. 5 14. 05 136. 2 72. 33 58. 35 17, 210 30. 0 21.0 21.0 1. 5 14.05 14. 05 30.0 28.0 21.0 1. 5 14 05 136. 2 96. 5 58. 35 18, 610 30. 0 28. 0 21. 0 1. 5 14.05 14. 05 V 30.0 35.0 21. 0 1. 5 14 05 136. 2 120.63 58. 35 20, 010 30. 0 35. 0 21. 0 1. 5 14. 05 14. 05 30. 0 42. 0 21. 0 1. 5 1 05 136. 2 144. 4 53. 35 21, 410 26. 0 39.0 1. 5 12.95 12. 26. 0 6. 5 39. 0 1. 5 12 95 118. 0 22. 4 108. 3 16, 890 26. 0 6. 5 39.0 1. 5 12.95 12.95 26.0 13. 0 39.0 1. 5 1 95 118.0 44. 8 108. 3 17,190 26. 0 13. 0 '39. 0 1. 5 12.95 12.95 26.0 26.0 39. 0 1. 5 12 95 118 0 89. 6 108 3 19, 790 26. 0 26. 0 39. 0 1. 5 12.95 12.95 26.0 39.0 39. 0 1. 5 12 95 118 0 134.4 108 3 21, 26. 0 39. 0 39. 0 l. 5 12. 95 12.95 26. 0 52.0 39.0 1. 5 12 95 118 0 179. 2 108 3 23, 990 26. 0 52. 0 39. 0 1. 5 12.95 12.95 26. 0 65. 0 39. 0 1. 5 12 95 118 0 224. 0 108 3 26, 490

TABLE X Max. Max. Ex. temp., pres Time, No. C. p. 8.1. 111s.

Water Kerosene 125-130 10-15 A Insoluble Insoluble. 125-130 10-15 Emulsifiable- D0. 125-130 7 10-15 do Do. 120-130 10-15 D0. -130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 130. 125-130 10-15 H 0--. D0. 125-130 10-15 Emulsifiable- Do. 125-130 10-15 Soluble- Do. 125-130 10-15 1 M D0. 125-130 10-15 1 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 1 D0. 125-130 10-15 2 D0. 125-130 10-15 2 Do. 125-130 10-15 A Do. 125-130 10-15 1 Do. 125-130 10-15 1 D0. 125-130 10-15 1 Do. 125-130 10-15 2 D0. 125-130 10-15 4% Soluble 125-130 10-15 1 Insoluble 125-130 10-15 1 D0. 125-130 10-15 1 D0. 125-130 10-15 1% D0. 125-130 10-15 3 Do. 125-130 10-15 6 Soluble 120-130 10-15 1 Insoluble 125-130 10-15 1 D0. 125-130 10-15 2 Do. 125-130 10-15 4% D0. 125-130 10-15 5 Soluble 125-130 10-15 7 D0. -150 10-15 Insoluble 145-150 10-15 Do. 145-150 10-15 D0. 145-150 10-15 Do. 145-150 10-15 Soluble 145-150 10-15 Do. 145-150 10-15 Insoluble 145-150 10-15 D0. 145-150 10-15 Do. 145-150 10-15 D0- 145-150 10-15 Soluble 145-150 10-15 Do. 145-150 10-15 Insoluble 145-150 10-15 D0. 145-150 10-15 Do. 145-150 10-15 Soluble 145-150 10-15 D0. 145-150 10-15 D0.

moved. Since the products per se are alkaline due to.

the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen'radical also. The preferred procedure isto ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid.

present is comparatively small and it need not be reequal to the causticsoda present. 1-

TABLE XI Max. Max. Solubility Ex. temp., pres., Time, No. C. p. s. i. hrs.

Water Xylene Kerosene -130 10-15 Emulsifiable. Insoluble. 125-130 10-15 (10 DO. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 DO. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 DO. 125-130 10-15 DO. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 D0. 125-130 10-15 Insoluble 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 D0. 125-130 10-15 Insoluble 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 D0. 125-130 10-15 Insoluble. 125-130 10-15 DO. 125-130 10-15 Do. 125-130 10-15 D0. 125-145 10-15 *DO. -150 10-15 DO. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 125-145 10-15 Do. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 125-145 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-150 10-15 D0. 145-125 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 7 Do. 125-130 10-15 D0. 125-130 10-15 D0. 145-125 10-15 D0. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 145-125 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 145-125 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 D0. 125-130 10-15 DO. -125 10-15 D0. 125-130 10-15 .Do. 125-130 10-15 Do. 125-130 10-15 .DD. 125-130 10-15 D0. 125-130 10-15 a ..D0. 150-130 10-15 D0. 125-130 10-15 .DO. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 Do. 4

TABLE XII Max. Max. Solubility Ex. temp., pres., Time, No. C. p. s. i. hrs.

Water Xylene Kerosene 150-125 -15 Inso1uble Soluble.

10-15 Insoluble 10-15 D0. 10-15 D0. 10-15 Soluble. 10-15 D0. 10-15 Do. 10-15 Insoluble 10-15 D0. 10-15 Soluble. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Insoluble. 10-15 D0. 10-15 D0. lO- D0. 10-15 D0. 10-15 I Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 3 D0. 10-15 8 do Do. 10-15 3% Insoluble Do.

125-130 10-15 4% do do Do PART 7 formaldehyde; said condensation reaction being conduct- As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and etfect to the instant process, noting only that where reference is made to Example 135 in said text beginning in column 15 and ending in column 18, reference should be to Example 60E, herein described.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a dernulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said step being that of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropy irnidine radical; and (c) ed at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble, said polyepoxides being free from reactive functional groups other. than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solventsoluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solventsoluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said first step susceptible,

2,171,4gssin which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and lowmelting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a diepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) an oxyalkylationsusceptible, fusible, nonoxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol- 36 forming reactivity; said reisn being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of re action; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with nonaryl hydroa: phile diepoxides characterized by the fact that the pre cursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently the radical in the diepoxide is water-soluble; said diepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal om'rane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and low-melting alpha-beta alkylene oxide having not more than 4 carbon,

atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide. a 4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5., A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by a 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a diepoxide, and (3) oxylkylation with a monoepoxide; said first step being that of (A) condensing (a) an oxyalkylation-sus ceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming'reactivity; said resin being derived by reaction between a difurictional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward i P Said e n be g ormed in the substantial 37 absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) reacting said resin condensate with a hydroxylated diepoxypolyglycerol having not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of acylationand oxyalkylation-susceptible solvent-soluble liquids and lowmelting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxidederived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

6. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei.

7. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted.

8. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde.

10. The process of claim 5 wherein th polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precusory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin is not over 5.

11. The process of claim 1 with the proviso that the hydrophil properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

12. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of Xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 Volumes of water.

14. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to pnoduce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 7 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 8 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

19. The process of claim 9 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in the equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

20. The process of claim 10 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS 2,395,739 Hersberger Feb. 26, 1946 2,454,541 Bock et al. Nov. 23, 1948 2,457,634 Bond et al. Dec. 28, 1948 2,589,198 Monson Mar. 11, 1952 2,695,889 De Groote Nov. 30, 1954 

1. A PROCESS FOR BREAKING PETROLUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID STEP BEING THAT OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE. FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECUALR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RRESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORM ING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 